The present invention relates to pesticidal compositions and pesticidal methods.
Hitherto, pesticides for controlling various pests such as agricultural and forestry pests, ectoparasites of animals and hygienically unfavorable pests have been developed. However, it cannot be said that old pesticides exhibit satisfactory effects in the practical use wherein pests in various growth stages exist.
The present invention provides pesticidal compositions and pesticidal methods which are very effective for controlling the pests in agricultural and forestry fields, such as whiteflies, and further effective for controlling ectoparasites of animals, hygienically unfavorable pests and the other various pests.
According to the present invention, a pesticidal composition comprising 4-phenoxyphenyl 2-(2-pyridyloxy)propyl ether and (E)-1-(2-chlorothiazol-5-ylmethyl)-3-methyl-2-nitroguanidine as active ingredients and a pesticidal method comprising utilizing 4-phenoxyphenyl 2-(2-pyridyloxy)propyl ether and (E)-1-(2-chlorothiazol-5-ylmethyl)-3-methyl-2-nitroguanidine together give satisfactory effect in practical use.
Namely, the present invention provides a pesticidal composition (hereinafter, referred to as the present pesticidal composition) comprising 4-phenoxyphenyl 2-(2-pyridyloxy)propyl ether (hereinafter, referred to as pyriproxyfen) and (E)-1-(2-chlorothiazol-5-ylmethyl)-3-methyl-2-nitroguanidine (hereinafter, referred to as chlothianidine) as active ingredients and a pesticidal method (hereinafter, referred to as the present pesticidal method) comprising utilizing pyriproxyfen and chlothianidine together.
Pyriproxyfen used in the present pesticidal composition and the present pesticidal method is a compound described in U.S. Pat. No. 4,751,225 specification and chlothianidine is a compound described in U.S. Pat. No. 5,034,404 specification. These compounds can be produced according to the descriptions in these specifications.
The combination of pyriproxyfen and chlothianidine produces a synergistic effect that is clearly larger than a sum of the sole effect of each compound as shown in the test examples described later.
In the present pesticidal composition and the present pesticidal method, pyriproxyfen and chlothianidine are combined and utilized in a ratio that can produce a synergistic effect. It is usually 0.01 to 30 parts by weight of chlothianidine, preferably 0.5 to 10 parts by weight based on 1 part by weight of pyriproxyfen.
The present pesticidal composition and the present pesticidal method can be applied for controlling various pests such as agricultural and forestry pests, ectoparasites of animals and hygienically unfavorable pests. Examples of the pest include arthropods such as insects and acarina and nematoda, namely Hemipteran pests such as Delphacidae (planthoppers) [e.g. Laodelphax striatellus (small brown planthopper), Nilaparvata lugens (brown planthopper) and Sogatella furcifera (white-backed rice planthopper)], Deltocephalidae (leafhoppers) [e.g. Nephotettix cincticeps and Nephotettix virescens], Aphididae (aphids) [e.g. Aphis gossypii (cotton aphids), Myzus persicae (green peach aphid), Aphis citricola, Lipaphis pserudobrassicae (turnip aphid), Nippolachnus piri, Toxoptera aurantii (black citrus apid) and Toxoptera ciidius (brown citrus apid)], stink bugs [e.g. Nezara antennata (green stink bug), Cletus punctiger, Riptortus clavetus (bean bug) and Plautia stali (oriental stink bug)], Aleyrodidae (whiteflies) [e.g. Trialeurodes vaporariorum (greenhouse whitefly), Bemisia tabaci (sweetpotato whitefly) and Bemisia argentifolli (silverleaf whitefly)], scales [e.g. Aonidiella aurantii (California red scale), Comstockaspis perniciosa (San Jose scale), Unaspis citri (citrus snow scale), Pseudaulacaspis pentagona (white peach scale), Saissetia oleae (brown olive scale), Lepidosaphes beckii (purple scale), Ceroplastes rubens (red wax scale) and Icerya purchasi (cottonycushion scale)], Tingidae (lace bugs) and Psyllidae (suckers); Lepidopteran pests such as Pyralidae [e.g. Chilo suppressalis (rice stem borer), Cnaphalocrocis medinalis (rice leafroller), Ostrinia nubilalis (European cornborer), Parapediasia teterrella (bluegrass webworm), Notarcha derogata (cotton leafroller) and Plodia interpunctella (Indian meal moth)], Noctuidae [e.g. Spodoptera litura (tobacco cutworm), Pseudaletia separata (rice armyworm), Mamestra brassicae (cabbage armyworm), Agrotis ipsilon (black cutworm), Trichoplusia spp., Heliothis spp. and Helicoverpa spp.], Pieridae [e.g. Pieris rapae], Tortricidae [e.g. Adoxophyes spp., Grapholita molesta (oriental fruit moth) and Cydia pomonella], Carposinidae [e.g. Carposina niponensis (peach fruit moth)], Lyonetiidae [e.g. Lyonetia spp.], Lymantriidae [e.g. Lymantria spp. and Euproctis spp.], Yponameutidae [e.g. Plutella xylostella], Gelechiidae [e.g. Pectinophora gossypiella (pink bollworm)], Arctiidae (tiger moths) [e.g. Hyphantria cunea (fall webworm)] and Tineidae [e.g. Tinea translucens (casemaking clothes moth) and Tineola bisselliella (webbing clothes moth)]; Dipteran pests such as Culex spp. [e.g. Culex pipiens pallens and Culex tritaeniorhynchus], Aedes spp. [e.g. Aedes albopictus], Anopheles spp. [e.g. Anopheles sinensis], Chironomidae (midges), Ceratopogonidae (biting midges) [e.g. Culicoides oxystoma], Muscidae [e.g. Musca domestica (housefly) and Muscina stabulans (false housefly)], Calliphoridae, Sarcophagidae, Fannia spp. (little house flies), Anthomyiidae [e.g. Delia platura (seedcorn maggot) and Delia antiqua (onion maggot)], Tephritidae (fruit flies), Drosophilidae (vinegar flies), Psychodidae (sand flies), Simuliidae (black flies), Tabanidae, Stomoxyidae (stable flies) [e.g. Haematobia irritans] and Agromyzidae (leafminer flies); Coleopteran pests such as corn rootworms [e.g. Diabrotica virgifera virgifera (western corn rootworm) and Diabrotica undecimpunctata howardi (southern corn rootworm)], Scarabaeidae [e.g. Anomala cuprea and Anomala rufocuprea], Curculionidae (weevils) [e.g. Sitophilus zeamais (maize weevil), Lissorhoptrus oryzophilus (ricewater weevil), Hypera pastica (alfalfa weevil) and Callosobruchuys chienensis (adzuki bean weevil)], Tenebrionidae (darkling beetles) [e.g. Tenebrio molitor (yellow mealworm) and Tribolium castaneum (red flour beetle)], Chrysomelidae (leaf beetles) [e.g. Aulacophora femoralis (cucurbit leaf beetle), Phyllotreta striolata (striped flea beetle) and Leptinotarsa decemlineata (Colorado beetle)], Anobiidae, Epilachna spp. [e.g. Epilachna vigintioctopunctata], Lyctidae (powderpost beetles), Bostrychidae, Cerambycidae and Paederus fuscipes; Dictyopteran pests such as Blattella germanica (German cockroach), Periplaneta fuliginosa (smokybrown cockroach), Periplaneta americana (American cockroach), Periplaneta brunnea (brown cockroach) and Blatta orientalis; Thysanopteran pests such as Thrips palmi, Thrips tabaci, Thrips hawaiiensis (flower thrips), Scirtothrips dorsalis (yellow tea thrips), Frankliniella intonsa (flower thrips), Frankliniella occidentalis (western flower thrips) and Ponticulothrips diospyrosi; Hymenopteran pests such as Formicidae (ants), Vespidae (hornets), Bethylidae and Tenthredinidae (sawflies) [e.g. Athalia japonica (cabbage sawfly)]; Orthopteran pests such as Gryllotalpidae (mole crickets) and Acrididae (grasshoppers); Siphonapteran pests such as Pulex irritans (human flea), Ctenocephalides felis (cat flea) and Ctenocephalides canis (dog flea); Anopluran pests such as Pediculus humanus corporis and Phthirus pubis (crab louse); Isopteran pests such as Reticulitermes speratus and Coptotermes formosanus; Acarina such as Tetranychidae (spider mites) [e.g. Tetranychus urticae (two-spotted spider mite), Tetranychus kanzawai (Kanzawa spider mite), Panonychus citri (citrus red mite), Panonychus ulmi (European red mite) and Oligonychus spp.], Eriophyidae [e.g. Aculops pelekassi (pink citrus rust mite) and Calacarus carinatus (purple tea mite)], Tarsonemidae [e.g. Polyphagotarsonemus latus], Tenuipalpidae (false spider mites), Tuckerellidae, Ixodidae [e.g. Haemaphysalis flava (Japanese tick), Haemaphysalis flava (yellow tick), Ixodes ovatus and Ixodes persulcatus], Acaridae [e.g. Tyrophagus putrescentiae (copra mite)], Dermanyssidae [e.g. Dermatophagoides farinae (American house dust mite), Dermatophagoides ptrenyssnus], Cheyletidae [e.g. Cheyletus eruditus, Cheyletus fortis, Cheyletus malaccensi and Cheyletus moorei] and chicken mites]; and Nematoda such as Pratylenchus coffeae (coffee root-lesion nematode), Pratylenchus fallax, Pratylenchus loosi, Pratylenchus vulnus (walnut root-lesion nematode), Heterodera glycines (soybean cyst nematode), Glohodera rostochiensis (potato cyst nematode), Meloidogyne hapla (northern root-knot nematode) and Meloidogyne incognita (southern root-knot nematode).
In the present pesticidal method, each of pyriproxyfen or its formulation and chlothianidine or its formulation can be used simultaneously, but it is convenient to use the present pesticidal composition in which pyriproxyfen and chlothianidine are mixed with each other in advance.
The present pesticidal composition comprises pyriproxyfen and chlothianidine as active ingredients and usually further comprises an inert carrier. The inert carrier can be solid carriers, liquid carriers and the like which are utilized for usual pesticidal formulations. The present pesticidal composition can optionally comprise formulation auxiliaries such as surfactant, dispersant, adhesive agent, stabilizer and propellant to be formulated to oil solution, emulsifiable concentrates, wettable powders, flowables such as aqueous suspension and aqueous emulsion, microcapsule formulation, spot-on formulation, pour-on formulation, shampoo formulation, granules, dusts, aerosol, ULV formulation, poison bait, sheet formulation and resin formulation.
The total amount of pyriproxyfen and chlothianidine in the present pesticidal composition is usually 0.01 to 90% by weight, preferably 0.1 to 80% by weight.
Examples of the solid carrier include fine powders and granules of clays such as kaolin clay, diatomaceous earth, bentonite, Fubasami clay and terra alba; synthetic hydrated silicon oxide; talc and the like; ceramics; the other inorganic minerals such as sericite, quartz, sulfur, activated carbon, calcium carbonate and hydrated silica; and chemical fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride. Examples of the liquid carriers include water; alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and methylnaphthalene; aliphatic hydrocarbons such as hexane, cyclohexane, kerosene and gas oil; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and isobutyronitrile; ethers such as diisopropyl ether and dioxane; acid amides such as N,N-dimethylformamide and N,N-dimethylacetamide; halogenated hydrocarbons such as dichloroethane, trichloroethane and carbon tetrachloride; dimethyl sulfoxide; and vegetable oils such as soybean oil and cottonseed oil.
Further, the present composition may be formulated by added a propellant such as flon gas, butane gas, liquefied petroleum gas, dimethyl ether and carbon dioxide thereto.
Examples of the surfactant include alkyl sulfate ester salts, alkylsulfonate salts, alkylarylsulfonate salts, alkylaryl ethers and polyoxyethylenated derivatives thereof, polyethyleneglycol ethers, polyvalent alcohol esters and sugar alcohol derivatives.
Examples of the other auxiliaries such as adhesive agents and dispersants include casein; gelatin; saccharides such as starch, gum arabic, cellulose derivatives and alginic acid; lignin derivatives; bentonite; and synthetic water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone and polyacrylic acids. Further, stabilizers including PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, fatty acids and fatty acid esters can be utilized as formulation auxiliaries.
Examples of the base materials for the poison bait include bait ingredients such as grain powder, vegetable oils, sugars and crystalline cellulose; antioxidants such as BHT and nordihydroguaiaretic acid; substances for preventing erroneous eating from children and pets such as red pepper powder; and attractants such as cheese flavor, onion flavor, leek flavor and peanut oil.
Examples of the base materials for resin formulations include olefin polymers, vinyl chloride polymers and polyurethanes. To these base materials, there can be added, if necessary, plasticizers such as phthalates and stearic acid; pest attractants such as pheromones; coloring agents with pest-attractive colors; and so on.
The resin formulations can be obtained by kneading the active ingredients into the base materials with a conventional kneader and then forming by injection, extrusion or compression molding. Further, they can be also obtained by supporting the active ingredients on the base materials which do not contain the active ingredients by impregnation, coating, printing or the like. In the operation, the active ingredients may be used in the form of oil solutions, emulsifiable concentrates, flowables or their dilutions. The resin formulations thus obtained can be formed through further steps, if necessary, such as shaping and cutting, into plates, films, tapes, nets, strings or the like, and can also be formed into sheets for mulching, attractive strings, supports for horticultural use, sheet formulations, wrapping films, animal collars and ear tags for animals.
The flowable formulations of the present pesticidal composition usually contain 1-75% by weight of the active ingredients, 0.5-15% by weight of dispersants, 0.1-10% by weight of suspension aids (e.g., protective colloids, thixotropy-conferring compounds), 0-10% by weight of auxiliaries (e.g., antifoaming agents, rust preventives, stabilizers, spreading agents, penetration aids, antifreezing agents, antibacterial agents, antifungal agents). The replacement of water with oils in which the active ingredients can hardly be dissolved makes it possible to produce oily suspensions. As the protective colloids, there can be used, for example, gelatin, casein, gums, cellulose ethers, polyvinyl alcohol and the like. The thixotropy-conferring compounds may include, for example, bentonite, alminum magnesium silicate, xanthan gum, polyacrylic acid and so on.
In the present pesticidal composition and the present pesticidal method, the other insecticide, nematocide, acaricide, repellent, fungicide, herbicide, plant growth regulator, synergist, fertilizer, soil improving agent or animal food may be used simultaneously.
Examples of the insecticide, nematocide and acaricide include pyrethroid compounds such as permethrin, cypermethrin, fenvarelate, esfenvarelate, fenpropathrin, biphenthrin, deltamethrin, fluvalinate, flucythrinate, allethrin, d-allethrin, prallethrin, cyphenothrin, phenothrin, resmethrin, tefluthrin, empenthrin, acrinathrin, cyhalothrin, cyfluthrin, etofenprox, halfenprox, silafluofen, tralomethrin, cycloprothrin, esbiothrin, transfluthrin, terallethrin, imiprothrin and 1-ethynyl-2-fluoro-2-pentenyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate; organophosphorus compounds such as cyanophos, fenthion, fenitrothion, parathion, methylparathion, pirimiphos-methyl, diazinon, isoxathion, pyridaphenthion, chlorpyrifos, chlorpyrifos-methyl, oxydeprofos, vamidothion, malathion, phenthoate, dimethoate, thiometon, disulfoton, phosalone, phosmet, methidathion, prothiofos, sulprofos, profenofos, azinphosmethyl, pyraclofos, calvinphos, salithion, tetrachlorvinphos, dichlorvos, monocrotophos, naled, dimethylvinphos, propaphos, acephate, metamidofos and ethion; carbamate compounds such as carbaryl, metolcarb, isoprocarb, fenobcarb, propoxur, XMC, ethiofencarb, bendiocarb, pyrimicarb, carbosulfan, carbofuran, benfuracarb, furathiocarb, methomyl, thiodicarb, oxamyl, alanycarb, fenothiocarb, metoxadiazone and fenothiocarb; nitroiminoimidazolidine derivatives; nereistoxin derivatives such as cartap, bensultap and thiocyclam; formamidine derivatives such as amitraz and chlordimeform; phenylpyrazole derivatives such as ethiprole; benzoylphenylurea compounds such as diflubenzuron, teflubenzuron, chlorfluazuron, flufenoxuron, triflumuron, hexaflumuron, lufenuron and novaluron; triazine derivatives such as cyromazine; thiadiazine derivatives such as buprofezine; juvenoid compounds such as methoprene, hydroprene, fenoxycarb and diofenolan; tebufenozide; methoxyfenozide; halofenozide; chromafenozide; chlorofenapir; phenisobromolate; quinomethionate; propargit; fenbutatin oxide; hexythiazox; clofentezine; pyridaben; fenpyroximate; tebufenpyrad; pyrimidifen; polynactin complex; milbemectin; avermectin; ivermectin and azadirachtin.
The present pesticidal method is an application of an effective amount of pyriproxyfen and chlothianidine to pest or a place where pests inhabit. Typical methods are explained as below.
In case of controlling agricultural or forestry pests by the present pesticidal method, the application rate of pyriproxyfen and chlothianidine is usually 10 g to 10000 g, preferably 100 g to 1000 g per 1 hectare at the total amount of the active ingredients. In the present pesticidal method, the concentration is usually 10 ppm to 1000 ppm at the total amount of the active ingredients, when the present pesticidal composition such as emulsifiable concentrates, wettable powders and flowables is diluted with water and applied. Granules and dusts of the present pesticidal composition are applied as they are.
In the present pesticidal method, pyriproxyfen and chlothianidine may be supplied to foliar application to plants those are crops to be protected from agricultural and forestry pests, or soil treatment to the surroundings of the plants for making the active ingredients absorbed from their roots. Soil treatment can also control agricultural and forestry pests those inhabit in soil. Further, the resin formulations formed to sheet or string can be applied by winding around the plants, setting or covering on the soil surface of the surroundings of the plants.
In case of controlling hygienically unfavorable pests by the present pesticidal method, pyriproxyfen and chlothianidine are usually applied indoors and the application rate is 0.1 mg to 1000 mg, preferably 0.5 mg to 200 mg per 1 m2 of the floor at the total amount of the ingredients. The application rate is also 0.01 mg to 300 mg, preferably 0.1 mg to 100 mg per 1 m3 of the space when spraying to the air. The concentration of the applied dilution is usually 0.1 ppm to 10000 ppm at the total amount of the active ingredients, when the present pesticidal composition such as emulsifiable concentrates, wettable powders and flowables is diluted with water and applied. Oil solutions, aerosols, smokings, ULV formulations and poison baits are applied as they are. When the present pesticidal compositions are directly applied to small animals for controlling ectoparasites of the animals such as dogs and cats, they are applied by conventional veterinary methods: for example, as tablets, by feed incorporation, as suppositories or by injection (e.g., intramuscular, subcutaneous, intravenous, intraperitoneal) for systemic control; or by spraying oily or aqueous liquid, by pour-on or spot-on treatment, or as shampoo formulations or resin formulations such as ear tags for non-systemic control. For such direct application to animal bodies, the amounts for application are usually 0.1 mg to 500 mg per 1 kg of the animal weight at the total amounts of the active ingredients.
The amounts or concentrations for application may vary depending upon type of formulations, times, places and methods of application, kinds of pests, degree of damage, and other factors; they can therefore be increased or decreased without limitation to the above ranges.